JP2005097352A - Epoxy resin composition, semiconductor sealing material, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To exhibit sufficient flame retardancy without using a halogen-based flame retardant, to reduce the amount of non-halogen-based flame retardant used, and to reduce the viscosity and speed of the composition. To provide an epoxy resin composition, a semiconductor encapsulating material, and a semiconductor device using the same, which have all the properties of curability (low epoxy equivalent) and high glass transition temperature of the cured product in a well-balanced manner.
An epoxy resin (A) containing a 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1), a curing agent (B), and a non-halogen flame retardant (C). An epoxy resin composition, a semiconductor sealing material using the epoxy resin composition, and a semiconductor device.
[Selection figure] None.

Description

  The present invention relates to an epoxy resin composition that exhibits excellent flame retardancy and can be suitably used for electronic component material applications, and a semiconductor sealing material and a semiconductor device using the same.

  Conventionally, epoxy resin compositions have been widely used in various industrial fields such as paints, adhesive properties, and electrical and electronic properties because they are excellent in adhesion, corrosion resistance, electrical properties, and the like of the cured products obtained. Among these, in the field of electronic materials such as semiconductors and printed wiring boards, they are used as sealing materials and substrate materials, and demands for higher performance are increasing with technological innovation in these fields. .

  For example, semiconductor packages have been rapidly reduced in size and thickness, and BGAs with excellent high-density mounting have been newly developed, and have become the mainstream of IC and LSI chip packages. In this package, warpage after molding has become a major problem, and a technique for increasing the glass transition temperature of a cured product obtained as a solution is adopted. The BGA has a chip mounted on one side of the package, and the conductor pattern on the package substrate is connected with a fine gold wire and then sealed with an epoxy resin composition or the like by transfer molding. There is a need for a low-viscosity resin composition that is difficult to deform.

  Moreover, when using an epoxy resin composition as a sealing material, halogen-type flame retardants, such as a bromine, are mix | blended with the antimony compound in order to provide a flame retardance. However, in recent environmental and safety efforts, environmentally and flame-resistant flame retardants that do not use halogen-based flame retardants that may cause dioxins and do not use antimony compounds that are suspected of carcinogenicity. There is a strong demand for the development of a conversion method. Further, non-halogenation of the semiconductor sealing material is expected to be a technology that greatly contributes to improvement of the reliability of the semiconductor device left at high temperature.

  As a method for obtaining flame retardancy with a non-halogen epoxy resin composition, for example, a method using red phosphorus (for example, see Patent Document 1), a method using a phosphoric ester compound (for example, see Patent Document 2). ), A method using magnesium hydroxide (for example, see Patent Document 3), and the like have been proposed. However, in any case, it is a combination with a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a biphenyl type epoxy resin, etc., which have been generally used in the past, and is sufficient in flame retardancy, for example, a general index In order to achieve V-0 grade of UL94 flame retardant test, 2 parts by weight or more for red phosphorus, 7 parts by weight or more for phosphoric acid ester compounds, 150 weights for magnesium hydroxide with respect to 100 parts by weight of the epoxy resin. It is necessary to add a large amount of these non-halogen flame retardants, and problems such as defects in the moldability in the sealing process and reliability of the semiconductor device are likely to occur, and improvements are eagerly desired. .

  Further, as a method for obtaining flame retardancy without using a flame retardant, for example, increasing aromaticity in an epoxy resin to be used has been proposed (see, for example, Patent Document 4). However, the cured product obtained using the epoxy resin composition described in Patent Document 1 reaches the V-0 class of UL-94, which is a flame retardant index, but is an essential epoxy resin used in the composition. The epoxy equivalent of 270 g / eq or more is inferior in curability, and for example, when mixed with another low epoxy equivalent epoxy resin, it is inferior in moldability and further obtained. It cannot be applied to the above-mentioned BGA where the glass transition temperature of the product is low and a high glass transition temperature of 160 ° C. or higher is required.

  Examples of the epoxy resin from which a cured product having a high glass transition temperature can be obtained include 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane and 1- (2,7-diglycidyloxy). The resin composition using a mixture of -1-naphthyl) -1- (2-glycidyloxy-1-naphthyl) alkane and 1,1-bis (2-glycidyloxy-1-naphthyl) alkane as an epoxy resin is disclosed. (For example, refer to Patent Document 5). However, although the cured product obtained using the epoxy resin composition described in Patent Document 2 has an exceptionally high glass transition temperature, it cannot obtain UL-94 V-0 class flame retardancy. Therefore, a cured product capable of exhibiting sufficient flame retardancy can be obtained using a non-halogen epoxy resin composition, and the resin composition has a low viscosity, a fast curing property (low epoxy equivalent), and a high glass of the cured product. The present condition is that the composition which has the characteristics of a transition temperature in a well-balanced manner has not yet been presented.

JP-A-8-151427 (page 2-4) JP-A-9-235449 (pages 5-6 and 10-12) JP 2002-212392 A (pages 8 and 10-12) JP-A-11-140277 (page 2-4) JP-A-4-217675 (page 3-7)

  An object of the present invention is to exhibit sufficient flame retardancy without using a halogen-based flame retardant, to reduce the amount of non-halogen-based flame retardant used, and to reduce the composition. An object of the present invention is to provide an epoxy resin composition, a semiconductor sealing material, and a semiconductor device using the same, which have a good balance between viscosity, fast curability (low epoxy equivalent), and high glass transition temperature of the cured product.

  As a result of intensive studies to solve the above problems, the present inventor has obtained an epoxy resin composition using 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane as the epoxy resin. I found out that the problem was solved.

  That is, the present invention relates to an epoxy resin (A) containing 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1), a curing agent (B), and a non-halogen flame retardant (C). The epoxy resin composition characterized by containing these, the semiconductor sealing material using the same, and a semiconductor device are provided.

  According to the present invention, the cured product is excellent in flame retardancy without using a halogen-based flame retardant, and the resin composition has low viscosity, fast curability (low epoxy equivalent), and high glass transition temperature of the cured product. Thus, it is possible to provide an epoxy resin composition, a semiconductor sealing material, and a semiconductor device using the same that have all of the above characteristics in a well-balanced manner.

  The epoxy resin (A) used in the present invention contains 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1). Examples of the 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane include, for example, the following general formula (1)

(Wherein, R represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or a hydroxyphenyl group).

  Specific examples of these structures include the following structural formulas (1-1) to (1-11).

  Among these 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkanes (a1), from the viewpoint of excellent fluidity, curability and heat resistance, the structural formula ( 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane represented by 1-1) is preferred.

  The 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) has an epoxy equivalent of 150 to 170 g / eq, an ICI viscosity at 150 ° C. of 2.0 to 6.0 poise, and water. It is preferable to use a degradable chlorine having a property value of 200 ppm or less because of excellent fluidity, curability and heat resistance.

  The 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) is obtained by, for example, reacting 1,1-bis (2,7-dihydroxy-1-naphthyl) alkane with epihalohydrin. Can be obtained.

  Examples of the method for producing the 1,1-bis (2,7-dihydroxy-1-naphthyl) alkane include a method of reacting 2,7-dihydroxynaphthalene with aldehydes.

  Although it does not restrict | limit especially as said aldehydes, For example, although formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, benzaldehyde, p-hydroxy benzaldehyde etc. are mentioned, the fluidity | liquidity, sclerosis | hardenability, and heat resistance of an epoxy resin (A) are mentioned. It is preferable to use formaldehyde from the point of being excellent, in which case 1,1-bis (2,7-dihydroxy-1-naphthyl) alkane is 1,1-bis (2,7-dihydroxy-1). -Naphthyl) methane.

  The catalyst used in the reaction is not particularly limited, and may be either a basic catalyst or an acidic catalyst. Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, hydroxide Alkali metal hydroxides such as calcium or alkaline earth metal hydroxides, or alkali metal carbonates such as sodium carbonate and potassium carbonate can be used. Acidic catalysts include sulfuric acid, hydrochloric acid, nitric acid, hydrobromic acid, perchloric acid and other mineral acids, p-toluenesulfonic acid, benzenesulfonic acid and other sulfonic acids, oxalic acid, succinic acid, malonic acid, monochloroacetic acid, Carboxylic acids such as dichloroacetic acid are used. Usually, the amount of these catalysts used is preferably 0.01 to 0.1 mol with respect to 1 mol of 2,7-dihydroxynaphthalene. Although it may be used more than that, a large amount of acid or alkali and extra time are required for the neutralization step, so that it may be determined appropriately.

  More specifically, the method of reacting the 2,7-dihydroxynaphthalene and the aldehyde is described in detail. For example, in an aqueous dispersion, 1 mol of 2,7-dihydroxynaphthalene is added in the presence of a basic catalyst or an acidic catalyst. On the other hand, aldehydes are added in an amount of 0.5 to 1.0 mol, preferably 0.5 to 0.55 mol, and stirred at a temperature of 30 to 100 ° C., preferably 60 to 80 ° C. for 0.5 to 3 hours. Thereafter, after neutralization, the product is filtered off, washed with water, dried and then dried to obtain the target compound.

  The reaction product thus obtained is not a novolak product composed of a mixture of a dimerization product, a trimerization product, a tetramerization product, a pentamerization product, etc., but is a dimerization product with a production rate of substantially 100%. Only 1-bis (2,7-diglycidyloxy-1-naphthyl) alkane is obtained.

  In the present invention, the 2,7-dihydroxynaphthalene may be used alone, but other phenols and naphthols may be partially used together. At this time, as other phenols and naphthols to be used in combination, β-naphthol is preferable from the viewpoint that the dimerized product is formed at a substantially 100% component ratio.

  The reaction products when β-naphthol is used in combination are 1,1-bis (2,7-dihydroxy-1-naphthyl) alkane and 1- (2,7-dihydroxy-1-naphthyl) -1- (2 -Hydroxy-1-naphthyl) alkane and 1,1-bis (2-hydroxy-1-naphthyl) alkane are a mixture of three kinds of dimerization products.

Subsequently, the 1,1-bis (2,7-dihydroxy-1-naphthyl) alkane thus obtained is reacted with epihalohydrone to give 1,1-bis (2,7-diglycidyloxy-1-naphthyl). ) The method for obtaining the alkane is not particularly limited. For example, the epihalohydrin is added in an amount of 1.5 to 20 with respect to 1 mol of the hydroxyl group of the 1,1-bis (2,7-dihydroxy-1-naphthyl) alkane. Mole, preferably 3.0 to 10.0 mol, can be easily produced by reacting at 20 to 120 ° C., preferably 50 to 80 ° C. for 2 to 7 hours in the presence of a base. (Hereinafter, the reaction of phenols with epihalohydrin is referred to as an epoxidation reaction.)
The base used in the epoxidation reaction is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate, and the like. Potassium and sodium hydroxide are preferred.

  As epihalohydrin, epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like are used, and epichlorohydrin is preferable from the viewpoint of industrial availability.

  By adjusting the excess of the number of moles of epihalohydrin with respect to the number of moles of hydroxyl groups of the 1,1-bis (2,7-dihydroxy-1-naphthyl) alkane, the molecular weight, epoxy equivalent, and melt viscosity of the resulting epoxy resin are adjusted. Can be adjusted. Lowering the molar excess of epihalohydrin increases the molecular weight of the epoxy resin, and conversely increases the molecular weight. As the molecular weight increases, the epoxy equivalent and the melt viscosity also increase, and the heat resistance of the cured product tends to gradually decrease. However, generally, when the excess of the number of moles of epihalohydrin exceeds 10 times, the molecular weight, epoxy equivalent, and melt viscosity do not change so much, the range of 10 times or less is preferable from the viewpoint of economy.

  Depending on the conditions of the epoxidation reaction, the obtained epoxy equivalent, melt viscosity and purity differ, but the epoxy equivalent is 150 to 170 g / eq, the ICI viscosity at 150 ° C. is 2.0 to 6.0 poise, and hydrolyzable chlorine is It is preferable to adjust so as to have a property value of 200 ppm or less.

  Further, 1,1-bis (2,7-dihydroxy-1-naphthyl) alkane and other hydroxy compounds such as 1- (2,7-dihydroxy-1-naphthyl) -1- (2-hydroxy-1) -Naphthyl) alkane or 1,1-bis (2-hydroxy-1-naphthyl) alkane as a raw material may be reacted with epihalohydrin, and in this case, the reaction product obtained is It becomes a mixture of glycidyl ether compounds. In addition, glycidyl etherified product of 1- (2,7-dihydroxy-1-naphthyl) -1- (2-hydroxy-1-naphthyl) alkane and 1,1-bis (2-hydroxy-1-naphthyl) alkane In the present invention, the glycidyl etherified product is classified into an epoxy resin other than 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) described later.

  In the epoxy resin (A) used in the present invention, the 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) is reduced in viscosity of the epoxy resin, for example, and is applicable to BGA. It is possible to use a bifunctional epoxy resin (a2) other than 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) for the purpose of improving the viscosity.

  The bifunctional epoxy resin (a2) is not particularly limited as long as it is a bifunctional epoxy resin made from divalent phenols. For example, bisphenol A, bisphenol F, hydroquinone, resorcin, dihydroxynaphthalene. Bis (4-hydroxyphenyl) menthane, bis (4-hydroxyphenyl) dicyclopentane, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether Bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) ) Sulfide, bis (4-H Loxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- Bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 4,4′dihydroxybiphenyl-3,3 ′, 5,5′-tetra Use epoxy resin made of methyl biphenyl, bis (hydroxynaphthyl) methane, 1,1'-binaphthol, 1,1'-bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, etc. be able to.

  Among these, tetramethylbiphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and dihydroxynaphthalene type epoxy resin are particularly preferable because of excellent fluidity, curability, moldability, heat resistance, and the like. Moreover, what has an epoxy equivalent in the range of 140-210 g / eq is further excellent in fluidity | liquidity, sclerosis | hardenability, a moldability, heat resistance, etc. These epoxy resins may be epoxidized using divalent phenols alone as described above, but previously mixed with 1,1-bis (2,7-dihydroxy-1-naphthyl) alkanes. Then, epoxidation may be performed.

  In addition, the 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) and the bifunctional epoxy resin (a2) are uniformly mixed in a molten state before preparing the composition. It is preferable to keep it.

  Here, the mixing ratio of 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) and bifunctional epoxy resin (a2) is such that the weight ratio is (a1) / (a2) = A range of 95/5 to 60/40 is preferable because workability, blocking resistance, and properties such as fluidity, moldability, curability, and heat resistance of the epoxy resin composition are excellent. Specifically, in addition to dramatically improving fluidity and curability by using 5% by weight or more of (a2) with respect to (a1), 40% by weight or less of (a2) with respect to (a1). By using in, the heat resistance is dramatically improved.

  Moreover, the epoxy resin composition of this invention is the bifunctionality added as needed with the said 1, 1-bis (2, 7- diglycidyl oxy- 1-naphthyl) alkane (a1) as an epoxy resin (A). In addition to the epoxy resin (a2), other than 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) and bifunctional epoxy resin (a2), as long as the effects of the present invention are not impaired. These epoxy resins may be used in combination.

  Various other epoxy resins can be used at this time, such as phenols such as phenol, о-cresol, and catechol, or naphthols such as hydroxynaphthalene and dihydroxynaphthalene, and aldehydes such as formaldehyde. Phenol novolac epoxy resin or polynaphthol novolak epoxy resin, which is a glycidyl etherified product of the reaction product obtained by condensation of phenols such as phenol, cresol and methyl-t-butylphenol with aromatic aldehydes such as hydroxybenzaldehyde Polyglycidyl ethers of polyphenols containing trityl skeletons; polyphenolic novolacs containing trimethyl skeletons, which are reaction products of polyphenols containing trityl skeletons and formaldehydes Polyglycidyl ethers; phenols such as phenol, o-cresol and catechol, or naphthols such as hydroxynaphthalene and dihydroxynaphthalene, and polyarachi which is a reaction product of xylylene dichloride, (hydroxymethyl) benzene and the like Polyglycidyl ethers of ruphenol resins or polyglycidyl ethers of polyaralkylnaphthol resins; phenols such as phenol, o-cresol and catechol; naphthols such as hydroxynaphthalene and dihydroxynaphthalene; and dicyclopentadiene and limonene An alicyclic hydrocarbon-containing polyphenol resin-type epoxy resin or polynaphthol resin-type epoxy resin, which is a glycidyl ether of a reaction product of an unsaturated alicyclic hydrocarbon with an alicyclic hydrocarbon-containing poly Phenolic resins;

Polyaliphatic hydrogen-containing polyphenol novolak resins or polyglycidyl ethers of polynaphthol novolak resins, which are the reaction products of polynaphthol resins and formaldehyde; obtained by condensation reaction of phenols or naphthols with aromatic carbonyl compounds Glycidyl ether compounds of polyperphenols and polyvalent naphthols that can be obtained;

Phloroglysin, tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,3-bis [(4-hydroxyphenyl) methyl] benzene, 1,4-bis Polyglycidyl ethers of trivalent or higher phenols having [(4-hydroxyphenyl) methyl] benzene or the like as a basic skeleton; glycidyl ether compounds derived from cyclic phenols such as calixarene;

p-aminophenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'diaminodiphenyl ether, 3,4'- Diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3- Aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, P-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m -Xylylenediamine, 1,4-cyclohexanebis (methylamino) ), 1,3-cyclohexanebis (methylamine), amine-based epoxy resins derived from N, N-diglycidylaniline, etc .; aroma such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, isophthalic acid Glycidyl ester compounds derived from aromatic carboxylic acids; hydantoin epoxy compounds derived from 5,5-dimethylhydantoin and the like; 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4 -(2,3-epoxypropyl) cyclohexyl] cycloaliphatic epoxy resins such as propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; unsaturated hydrocarbon compounds such as polybutadiene Aliphatic epoxide obtained by oxidizing the double bond Shi resins. One or two or more of these epoxy resins may be used.

  Among these, a novolac type epoxy resin is preferable for the purpose of improving heat resistance, and a dicyclopentadiene-modified phenol type epoxy resin is preferably used in combination for the purpose of improving moisture resistance.

  Other epoxy resins other than the 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) and the bifunctional epoxy resin (a2) are used as long as the effects of the present invention are not impaired. obtain. Specifically, it is less than 50% by weight in all epoxy resin components (epoxy resin (A)), that is, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) and A range in which the total weight of the bifunctional epoxy resin (a2) is 50% by weight or more with respect to the entire epoxy resin (A) is preferable.

  The curing agent (B) used in the epoxy resin composition of the present invention is not particularly limited, and various curing agents conventionally used as curing agents for epoxy resins can be used. For example, amine compounds , Acid anhydride compounds, amide compounds, phenol compounds, and the like.

Specific examples of the curing agent (B) include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, and phthalic anhydride. Acid, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac resin, cresol novolac Resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol Tan resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, aminotriazine-modified phenol resin and the like, imidazole, Examples thereof include BF ₃ -amine complexes and guanidine derivatives, and these may be used alone or in combination of two or more.

  Among these, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol, because of the excellent flame retardancy of the resulting epoxy resin composition -Phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, and aminotriazine-modified phenol resin are preferable, particularly having a hydroxyl group by a linking group containing an aromatic ring having no hydroxyl group It is preferably a polyvalent aromatic compound containing a structure in which aromatic rings are linked. For example, an aromatic hydrocarbon formaldehyde resin-modified phenol resin, a phenol aralkyl resin (common name, Iroc resin), naphthol aralkyl resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine Modified phenolic resins (polyhydric phenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.) are preferred.

  Although it does not restrict | limit especially as a compounding quantity of the hardening | curing agent (B) in the epoxy resin composition of this invention, From the point that the mechanical physical property etc. of the obtained hardened | cured material are favorable, of epoxy resin (A). The amount by which the active group in the curing agent is 0.7 to 1.5 equivalents with respect to 1 equivalent of epoxy group is preferable.

  Moreover, a hardening accelerator can also be suitably used together with the epoxy resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5,4,0] -undecene (DBU) is preferred.

  The non-halogen flame retardant (C) used in the present invention is blended into a resin composition or the like to impart flame retardancy, and is not limited as long as it does not substantially contain a halogen atom. It is possible to use without.

  The flame retardant resin composition containing substantially no halogen atom means a resin composition exhibiting sufficient flame retardancy even if a halogen-based compound is not added for the purpose of imparting flame retardancy. The trace amount halogen of about 5000 ppm or less derived from epihalohydrin contained in the epoxy resin may be contained.

  The non-halogen flame retardant (C) is a compound that does not substantially contain a halogen atom such as chlorine or bromine and has a function as a flame retardant or a flame retardant aid. For example, phosphorus flame retardant (c1), nitrogen flame retardant (c2), silicone flame retardant (c3), inorganic flame retardant (c4), organometallic salt flame retardant (c5), etc. There are no restrictions on the use of these, and they may be used alone or in combination with a plurality of flame retardants of the same system, or a combination of flame retardants of different systems may be used. It is.

  As the phosphorus-based flame retardant (c1), both inorganic and organic compounds can be used as long as they are compounds containing phosphorus atoms. Examples of the inorganic compound include phosphoric acids such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, which may be surface-treated for the purpose of preventing hydrolysis and the like. Examples thereof include inorganic nitrogen-containing phosphorus compounds such as ammonium and phosphoric acid amide.

  Examples of the surface treatment method of red phosphorus include (1) coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof. A method of treating, (2) a method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide and titanium hydroxide, and a thermosetting resin such as phenol resin, (3) magnesium hydroxide In addition, there is a method of doubly coating with a thermosetting resin such as a phenol resin on a coating of an inorganic compound such as aluminum hydroxide, zinc hydroxide, titanium hydroxide, and any one of (1) to (3) What was processed by the method of can also be used.

  Examples of the organic phosphorus compounds include phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, and organic nitrogen-containing phosphorus compounds.

  Specific examples of the phosphate ester compound include triphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis (di2,6-xylenol phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate). ), Resorcinyl diphenyl phosphate and the like.

  Specific examples of the phosphonic acid compound include phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, and phosphonic acid metal salts described in JP-A No. 2000-226499.

  Specific examples of the phosphinic acid compound include diphenylphosphinic acid, methylethylphosphinic acid, a compound described in JP-A-2001-55484, 9,10-dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = Examples thereof include cyclic organophosphorus compounds such as 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  Specific examples of the phosphine oxide compound include triphenylphosphine oxide, tris (3-hydroxypropyl) phosphine oxide, diphenylphosphinyl hydroquinone, JP-A No. 2000-186186, JP-A No. 2002-080484, JP-A No. 2002. -097248 gazette etc. are mentioned.

  Specific examples of the phosphorane compound include compounds described in JP-A No. 2000-281871.

  Examples of organic nitrogen-containing phosphorus compounds include JP 2002-60720, JP 2001-354686, JP 2001-261792, JP 2001-335703, JP 2000-103939, and the like. And the phosphazene compounds described.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant (c1), other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, the epoxy resin (A) In 100 parts by weight of the epoxy resin composition containing all of the curing agent (B), flame retardant (C) and other fillers and additives, 0.1% is used when red phosphorus is used as the flame retardant (C). It is preferable to mix | blend in the range of -2.0 weight part, and when using an organophosphorus compound, it is similarly preferable to mix | blend in the range of 0.1-10.0 weight part, Especially 0.5-6. It is preferable to mix in the range of 0 part by weight.

  Further, the method of using the phosphorus flame retardant (c1) is not particularly limited. For example, JP 2002-080566 A, JP 2002-053734 A, JP 2000-248156 A, The combined use of hydrotalcite described in Kaihei 9-235449, the combined use of magnesium hydroxide described in JP-A-2001-329147, etc., JP-A-2002-23989, JP-A-2001-323134, etc. A combination of the above described boron compounds, a combination of zirconium oxide described in JP-A No. 2002-069271, etc., a combination of black dyes described in JP-A No. 2001-123047, etc., and JP-A No. 2000-281873 Combined use of calcium carbonate, combined use of zeolite described in JP 2000-281873 A, etc. Combined use of zinc molybdate as described in JP 2000-248155 A, etc., combined use of activated carbon as described in JP 2000-212392 A, JP 2002-348440 A, JP 2002-265758 A, 2002 Conventional methods such as surface treatment methods described in Japanese Patent No. 180053, Japanese Patent Application Laid-Open No. 2001-329147, Japanese Patent Application Laid-Open No. 2001-226564, Japanese Patent Application Laid-Open No. 11-269345, and the like can be applied.

  The nitrogen-based flame retardant (c2) is not particularly limited as long as it is a compound containing a nitrogen atom, and examples thereof include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, triazine compounds, A cyanuric acid compound and an isocyanuric acid compound are preferable.

  Specific examples of the triazine compound include, for example, melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and derivatives thereof. For example, (1) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, melam sulfate, (2) phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, and melamine, benzoguanamine, acetoguanamine, formguanamine, etc. A co-condensate of melamines and formaldehyde, (3) a mixture of the co-condensate of the above (2) and a phenol resin such as a phenol formaldehyde condensate, (4) the above (2), (3) is further paulownia oil, Modified with isomerized linseed oil, etc. And the like.

  Specific examples of the cyanuric acid compound include cyanuric acid, melamine cyanurate, diallyl monoglycidyl isocyanuric acid, monoallyl diglycidyl isocyanuric acid, and the like.

  Specific examples of the isocyanuric acid compound include tris (β-cyanoethyl) isocyanurate.

Further, the compound containing a nitrogen atom has a functional group such as —OH, —NH ₂ , —NCO, —COOH, —CHO, —SH, methylol, acrylate, methacrylate, silyl, glycidyl group or epoxy group. May be.

  The amount of the nitrogen-based flame retardant (c2) is appropriately selected depending on the type of the nitrogen-based flame retardant (c2), other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, in the range of 0.05 to 10 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the epoxy resin (A), the curing agent (B), the flame retardant (C), and other fillers and additives. It is preferable to mix | blend with 0.1 to 5 weight part especially.

  Further, the method of using the nitrogen-based flame retardant (c2) is not particularly limited. For example, a combination of metal hydroxides described in JP 2001-234036 A, JP 2002-003577 A, and the like. Conventional methods such as the combined use of molybdenum compounds described in JP-A-2001-098144 and the like can be applied.

  The silicone flame retardant (c3) is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  Specific examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, polyether-modified silicone oil, and the like.

  Specific examples of the silicone rubber include methyl silicone rubber and methylphenyl silicone rubber.

  Specific examples of the silicone resin include methyl silicone, methyl phenyl silicone, and phenyl silicone.

The organic compound containing a silicon atom has a functional group such as —OH, —NH ₂ , —NCO, —COOH, —CHO, —SH, methylol, acrylate, methacrylate, silyl, glycidyl group or epoxy group. You may do it.

  The amount of the silicone-based flame retardant (c3) is appropriately selected depending on the type of the silicone-based flame retardant (c3), the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, in the range of 0.05 to 20 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the epoxy resin (A), the curing agent (B), the flame retardant (C), and other fillers and additives. It is preferable to mix with.

  Further, the method of using the silicone flame retardant (c3) is not particularly limited. For example, the use of a molybdenum compound described in JP-A-2001-011288, JP-A-10-182941, etc. Conventional methods such as the combined use of the described alumina can be applied.

  Examples of the inorganic flame retardant (c4) include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low-melting glass.

  Specific examples of the metal hydroxide include, for example, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, JP 2002-212391 A, and JP 2001. Examples thereof include composite metal hydroxides described in JP-A No. 335681 and JP-A No. 2001-32050.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The amount of the inorganic flame retardant (c4) is appropriately selected depending on the type of the inorganic flame retardant (c4), the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, in the range of 0.05 to 20 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the epoxy resin (A), the curing agent (B), the flame retardant (C), and other fillers and additives. It is preferable to mix | blend with 0.5 to 15 weight part especially.

  Further, the method for using the inorganic flame retardant (c4) is not particularly limited. For example, a method for controlling the specific surface area described in JP-A No. 2001-226564, JP-A No. 2000-19595, JP-A-2000-191886, JP-A-2000-109647, JP-A-2000-038776, etc., methods for controlling the shape, particle size and particle size distribution, JP-A-2001-32050, JP-A-2000 No. 095956, JP-A-10-279813, JP-A-10-251486, etc., surface treatment, nitric acid described in JP-A-2002-030200, JP-A-2001-279063, etc. Combined use of metal salts, combined use of zinc borate described in JP 2001-049084 A, JP 2000-1959 In combination with inorganic powders described in No. 4 etc., in combination with butadiene rubber described in JP 2000-156437 A, etc., high acid value polyethylene wax and long chain alkyl phosphates described in JP 2000-053875 A, etc. Conventional methods such as the combined use of a series compound can be applied.

  Examples of the organometallic salt flame retardant (c5) include ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organocobalt salt compound, organosulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound. Examples thereof include an ionic bond or a coordinate bond compound.

  Specific examples of the acetylacetonate metal complex include compounds described in JP-A No. 2002-265760.

  Specific examples of the organometallic carbonyl compound include compounds described in JP-A No. 2002-371169.

  Specific examples of the organic cobalt salt compound include, for example, a cobalt naphthenic acid complex, a cobalt ethylenediamine complex, a cobalt acetoacetonate complex, a cobalt piperidine complex, a cobalt cyclohexanediamine complex, a cobalt tetraazacyclotetradodecane complex, and a cobalt ethylenediaminetetraacetic acid complex. , Cobalt tetraethylene glycol complex, cobalt aminoethanol complex, cobalt cyclohexadiamine complex, cobalt glycine complex, cobalt triglycine complex, cobalt naphthidirine complex, cobalt phenanthroline complex, cobalt pentanediamine complex, cobalt pyridine complex, cobalt salicylic acid complex, cobalt Salicylaldehyde complex, cobalt salicylideneamine complex, cobalt complex porphyrin, cobalt thiourea complex And the like can be given.

  Specific examples of the organic sulfonic acid metal salt include potassium diphenylsulfone-3-sulfonate.

  Specific examples of the compound in which the metal atom and the aromatic compound or heterocyclic compound are ion-bonded or coordinate-bonded include compounds described in JP-A-2002-226678.

  The amount of the organic metal salt flame retardant (c5) is appropriately selected depending on the type of the organic metal salt flame retardant (c5), other components of the epoxy resin composition, and the desired degree of flame retardancy. However, for example, 0.005 to 10 in 100 parts by weight of an epoxy resin composition containing all of the epoxy resin (A), the curing agent (B), the flame retardant (C), and other fillers and additives. It is preferable to mix in the range of parts by weight.

  Various compounding agents, such as a silane coupling agent, an ion trap agent, a mold release agent, and a pigment, can be added to the epoxy resin composition of the present invention as necessary.

  As for the epoxy resin composition of this invention, the shaping | molding hardened | cured material can be easily obtained by thermosetting. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Applications of the epoxy resin composition of the present invention include semiconductor sealing materials, resin compositions used for laminates and electronic circuit boards, resin casting materials, adhesives, interlayer insulation materials for build-up substrates, insulation paints Among these, it can be suitably used for a semiconductor sealing material.

  The semiconductor encapsulant material of the present invention further comprises an inorganic filler (D) in addition to the epoxy resin (A), the curing agent (B) and the non-halogen flame retardant (C) described above. It can be obtained by adding the components and mixing well until uniform using an extruder, kneader, roll or the like.

  Examples of the inorganic filler (D) include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When the blending amount of the filler (D) is particularly large, it is preferable to use fused silica. The fused silica can be used in either crushed or spherical shape, but the blending amount is increased and the melt viscosity of the molding material is increased. In order to suppress the increase in the amount, it is particularly preferable to use mainly spherical ones. In order to further increase the blending amount of the spherical silica, it is preferable that the particle size distribution of the spherical silica is appropriately adjusted so that the average particle size is 5 to 30 μm. The filling rate is particularly preferably 65 to 95% by weight with respect to the total amount of the epoxy resin composition from the viewpoint of good flame retardancy. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can also be used.

  The semiconductor device of the present invention uses the semiconductor encapsulant material, for example, molds the material as a semiconductor package molding by a casting, transfer molding machine, injection molding machine, etc. It can be obtained by heating for 10 hours.

  When the epoxy resin composition of the present invention is used as a resin composition for electronic circuit boards, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone. Can be manufactured. The amount of the solvent used in this case is usually 10 to 70% by weight, preferably 15 to 65% by weight, and particularly preferably 35 to 65% by weight in the resin composition for electronic circuit boards. In addition, as a method of obtaining the molded cured product, the resin composition for an electronic circuit board is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and dried by heating. After obtaining and laminating, a method of hot press molding it can be mentioned. Specific examples of the electronic circuit board include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.

  Further, when the epoxy resin composition of the present invention is used as a coating material such as an adhesive or paint, the composition may be melted and coated, or a solution obtained by dissolving the composition in the solvent is usually used. After coating by this method, the solvent may be removed by drying to be cured. At this time, the curing catalyst may be used as necessary. Moreover, you may mix the said inorganic filler etc.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “part” and “%” are based on weight unless otherwise specified.
Synthesis of Epoxy Resin (A) Synthesis Example 1
To a stirrer, thermometer, and 4-neck flask, 320 g (2 mol) of 2,7-dihydroxynaphthalene and 320 g of isopropyl alcohol were added and mixed well. Thereafter, 3.3 g of 49% NaOH was added and the temperature was raised to 70 ° C. Next, 81 g of 37% formalin was added dropwise over 1 hour while maintaining the liquid temperature at 70 ° C. Thereafter, stirring was continued at 70 ° C. for 2 hours to complete the dimerization reaction. 1850 g (20 mol) of epichlorohydrin was added thereto, and 360 g (4.4 mol) of 49% NaOH was added dropwise at 50 ° C. over 3 hours. Thereafter, stirring was continued at 50 ° C. for 1 hour to complete the epoxidation reaction, stirring was stopped, and the lower layer was discarded. Next, after excess epichlorohydrin was recovered by distillation, 1000 g of MIBK was added to dissolve the crude resin. 30% of 10% NaOH was added thereto and stirred at 80 ° C. for 3 hours. The stirring was stopped and the lower layer was discarded. 300 g of water was added thereto and washed twice, followed by dehydration-filtration-desolvation to obtain 501 g of the desired epoxy resin (A-1). This epoxy resin had an epoxy equivalent of 161 g / eq and an ICI viscosity at 150 ° C. of 3.8 poise.

Synthesis example 2
In a container equipped with a stirrer, 320 g of the epoxy resin (A-1) synthesized in Production Example 1 and 80 g of bisphenol F-type liquid epoxy resin having an epoxy equivalent of 170 g / eq were placed, heated to 150 ° C., and stirred for 30 minutes. And uniformly mixed to obtain 400 g of the desired epoxy resin (A-2). The epoxy equivalent of the epoxy resin was 163 g / eq, and the ICI viscosity at 150 ° C. was 0.9 poise.

Synthesis example 3
The target epoxy was prepared in the same manner as in Production Example 2, except that 300 g of the epoxy resin (A-1) was used and 100 g of a tetramethylbiphenol type liquid epoxy resin having an epoxy equivalent of 195 g / eq was used instead of the bisphenol F type liquid epoxy resin. 400 g of resin (A-3) was obtained. The epoxy equivalent of the epoxy resin was 168 g / eq, and the ICI viscosity at 150 ° C. was 0.9 poise.

Synthesis example 4
Target epoxy resin as in Production Example 2 except that 280 g of epoxy resin (A-1) and 120 g of tetramethylbiphenol type epoxy resin having an epoxy equivalent of 195 g / eq instead of bisphenol F type liquid epoxy resin were used. (A-4) 400 g was obtained. The epoxy equivalent of the epoxy resin was 170 g / eq, and the ICI viscosity at 150 ° C. was 0.8 poise.

Synthesis example 5
Production Example Except for using 320 g of epoxy resin (A-1) and 80 g of bisphenol A type liquid epoxy resin 1,6-dihydroxynaphthalene type epoxy resin having an epoxy equivalent of 188 g / eq instead of bisphenol F type liquid epoxy resin. In the same manner as in Example 2, 400 g of the target epoxy resin (A-5) was obtained. The epoxy equivalent of the epoxy resin was 166 g / eq, and the ICI viscosity at 150 ° C. was 1.0 poise.

Synthesis Example 6
The target epoxy resin was the same as Production Example 2 except that 280 g of epoxy resin (A-1) was used and 120 g of bisphenol A type liquid epoxy resin having an epoxy equivalent of 188 g / eq was used instead of bisphenol F type liquid epoxy resin. (A-6) 400 g was obtained. The epoxy equivalent of the epoxy resin was 168 g / eq, and the ICI viscosity at 150 ° C. was 0.7 poise.

Synthesis example 7
The purpose was the same as in Production Example 2 except that 320 g of epoxy resin (A-1) was used and 80 g of 1,6-dihydroxynaphthalene type epoxy resin having an epoxy equivalent of 188 g / eq instead of bisphenol F type liquid epoxy resin was used. Of epoxy resin (A-7) was obtained. The epoxy equivalent of the epoxy resin was 159 g / eq, and the ICI viscosity at 150 ° C. was 1.1 poise.

Synthesis example 8
Synthesis of a phenoxyphosphazene compound having a cross-linked structure by paraphenylene 103.5 g (1.1 mol) of phenol, sodium hydroxide in a 2 liter four-necked flask equipped with a stirrer, thermometer, reflux device and distillation tube A toluene solution of sodium phenolate was prepared by charging 44.0 g (1.1 mol), 50 g of water, and 500 ml of toluene, and heating to reflux to remove only water from the system.

  In parallel to the above reaction, a 2 liter four-necked flask equipped with the same apparatus was charged with 16.5 g (0.15 mol) of hydroquinone, 94.1 g (1.0 mol) of phenol, 31.1 g of lithium hydroxide ( 1.3 mol), water (52 g) and toluene (600 ml) were charged, heated to reflux and only water was removed from the system to prepare a toluene solution of hydroquinone and a lithium salt of phenol. Dichlorophosphazene oligomer (mixture of 72% trimer, 15% tetramer, 8% pentamer, 8% hexamer, 3% trimer, 2% octamer to 2%) was added to this toluene solution. 580 g of a 20% chlorobenzene solution of 1.0 unit mol) was added dropwise at 30 ° C. or lower under stirring, followed by stirring reaction at 110 ° C. for 4 hours. Next, after the toluene solution of sodium phenolate prepared previously was added with stirring, the reaction was continued at 110 ° C. for 8 hours. After completion of the reaction, the reaction mixture was washed 3 times with 1.0 liter of 3% aqueous sodium hydroxide solution and then washed 3 times with 1.0 liter of water, and then the organic layer was concentrated under reduced pressure. The obtained product was concentrated to dryness at 80 ° C. and 266 Pa or less to obtain 211 g of white powder.

The obtained white powder has a hydrolyzable chlorine content of 0.01% or less. From the phosphorus content and the CHN elemental analysis value, the crosslinked phenoxyphosphazene compound (c1-1) [N = P (—Op-Ph— O-) _0.15 (-O-Ph) _1.7 ].

Synthesis Example 9
Synthesis of phenoxyphosphazene compound having a crosslinked structure by 2,2-bis (p-oxyphenyl) isopropylidene group In a 1 liter four-necked flask equipped with a stirrer and a thermometer, 65.9 g (0.7 mol) of phenol Then, 500 ml of toluene was squeezed, and 14.9 g (0.65 mol) of metallic sodium was finely cut and added while maintaining the internal liquid temperature at 25 ° C. with stirring. Stirring was continued for 8 hours at 77-113 ° C. after completion of the addition until the metal sodium completely disappeared.

  In parallel with the above reaction, 57.1 g (0.25 mol) of bisphenol A, 103.5 g (1.1 mol) of phenol and 800 ml of tetrahydrofuran (THF) were added to a 3 liter four-necked flask equipped with a stirrer and a thermometer. Then, 11.1 g (1.6 mol) of metallic lithium was finely cut and charged while maintaining the internal liquid temperature at 25 ° C. with stirring. After completion of the addition, stirring was continued for 8 hours until the metallic lithium completely disappeared at 61 to 68 ° C. Dichlorophosphazene oligomer (mixture of trimer 72%, tetramer 15%, pentamer 8%, heptamer 3%, octamer 2%) was added to this slurry solution (115.9 g) While stirring, 386 g of a 30% chlorobenzene solution of 1.0 unit mol) was added dropwise over 1 hour while keeping the internal liquid temperature at 20 ° C. or lower, and reacted at 80 ° C. for 4 hours. Next, a sodium phenolate solution prepared separately was added over 1 hour while maintaining the internal liquid temperature at 20 ° C. with stirring, and then reacted at 80 ° C. for 10 hours. After completion of the reaction, the reaction mixture was concentrated to remove THF, and 1 liter of toluene was newly added. The toluene solution was washed 3 times with 1 liter of 2% NaOH and then 3 times with 1 liter of water, and then the organic layer was concentrated under reduced pressure. The obtained product was concentrated to dryness at 80 ° C. and 266 Pa or less to obtain 230 g of white powder.

The hydrolyzable chlorine of the obtained white powder is 0.01% or less. From the phosphorus content and the CHN elemental analysis value, the crosslinked phenoxyphosphazene compound (c1-2) [N = P (—O—Ph—C ( CH ₃₎ was confirmed _{2 -Ph-O-)} it is _{0.25 (-O-Ph) 1.50]} .

Examples 1-19 and Comparative Examples 1-6
Various materials shown in the following Tables 4 to 7 were used, and melt-kneaded at a temperature of 100 ° C. for 10 minutes using two rolls to obtain an epoxy resin composition. This was press-molded at 180 ° C. for 10 minutes, and then further cured at 180 ° C. for 5 hours, and then a test piece was prepared for the following test. A test was conducted.

  Glass transition temperature: Measured using a viscoelasticity measuring device (solid viscoelasticity measuring device RSAII manufactured by Rheometric Co., Ltd., double currant lever method; frequency 1 Hz, temperature rising rate 3 ° C./min).

  Moisture absorption rate (%): The weight increase rate after treatment for 300 hours under the condition of 85 ° C./85% RH was determined.

  Flame retardancy: Based on the UL-94 test method, a flame test was performed using five test pieces having a thickness of 1.6 mm.

  The obtained results are shown in Tables 4-7. In addition, the material used for the Example and the comparative example is shown to Tables 1-3.

Examples 1 to 19 using the epoxy resin composition of the present invention exhibit sufficient flame retardancy in the obtained cured product and have a high glass transition temperature of 160 ° C. or higher, and are semiconductor sealing materials, particularly BGA type. It was confirmed that it can be suitably used for the semiconductor device. On the other hand, Comparative Examples 1 to 3 are insufficient in flame retardancy of the resulting cured products despite the addition of non-halogen flame retardants, and Comparative Examples 5 and 6 have sufficient flame retardancy. I can't get it. Further, as is clear from Comparative Example 4 where the curing rate is slow, it was confirmed that the epoxy resin composition used in the Comparative Example was not at a level that was sufficiently satisfactory in the performance of the cured product.

Claims (16)

It contains an epoxy resin (A) containing 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1), a curing agent (B), and a non-halogen flame retardant (C). An epoxy resin composition. As the epoxy resin (A), in addition to 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1), the 1,1-bis (2,7-diglycidyloxy-1- The epoxy resin composition of Claim 1 which uses together bifunctional epoxy resin (a2) other than a naphthyl) alkane (a1). The weight ratio of 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) to the bifunctional epoxy resin (a2) is (a1) / (a2) = 95 / 5-60 The epoxy resin composition according to claim 2, which is in the range of / 40. The total weight of the 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) and the bifunctional epoxy resin (a2) is 50% by weight or more based on the entire epoxy resin (A). The epoxy resin composition according to claim 2. The bifunctional epoxy resin (a2) is at least one epoxy resin selected from the group consisting of tetramethylbiphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and dihydroxynaphthalene type epoxy resin. 2. The composition according to 2. 6. The polyvalent aromatic compound according to claim 1, wherein the curing agent (B) is a polyvalent aromatic compound having a structure in which an aromatic ring having a hydroxyl group is linked by a linking group having an aromatic ring having no hydroxyl group. Epoxy resin composition. The non-halogen flame retardant (C) is a phosphorus flame retardant (c1), a nitrogen flame retardant (c2), a silicone flame retardant (c3), an inorganic flame retardant (c4), and an organic metal salt flame retardant (c5). The epoxy resin composition according to claim 1, which is at least one flame retardant selected from the group consisting of: The non-halogen flame retardant (C) is a phosphorus flame retardant (c1), and the phosphorus flame retardant (c1) is red phosphorus, phosphate ester compound, phosphonic acid compound, phosphinic acid compound, phosphine oxide compound, phosphorane. The epoxy resin composition according to claim 7, which is one or more compounds selected from the group consisting of a compound and a nitrogen-containing phosphorus compound. The non-halogen flame retardant (C) is a nitrogen flame retardant (c2), and the nitrogen flame retardant (c2) is one or more compounds selected from the group consisting of triazine compounds, cyanuric acid compounds and isocyanuric acid compounds The epoxy resin composition according to claim 7. The non-halogen flame retardant (C) is a silicone flame retardant (c3), and the silicone flame retardant (c3) is one or more compounds selected from the group consisting of silicone oil, silicone rubber and silicone resin. The epoxy resin composition according to claim 7. The non-halogen flame retardant (C) is an inorganic flame retardant (c4), and the inorganic flame retardant (c4) is a metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound and low The epoxy resin composition according to claim 7, which is one or more compounds selected from the group consisting of melting point glasses. The organometallic salt flame retardant (c5) is ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organocobalt salt compound, organosulfonic acid metal salt, and metal atom and aromatic compound or heterocyclic compound are ionically bonded or arranged. The epoxy resin composition according to claim 7, wherein the epoxy resin composition is at least one selected from the group consisting of coordinately bonded compounds. Furthermore, the epoxy resin composition as described in any one of Claims 1-12 containing an inorganic filler (D). The semiconductor sealing material using the epoxy resin composition of any one of Claims 1-13. A semiconductor device using the semiconductor sealing material according to claim 14. 16. The semiconductor device according to claim 15, which is a BGA type.